Sundmacher NTNU 2007

Electrochemical Energy Conversion
using Fuel Cell Systems

Kai Sundmacher1,2
1 Max-Planck-Institutefor Dynamics of Complex Technical Systems, Magdeburg
2 Otto von Guericke University Magdeburg, Process Systems Engineering
NTNU, 29 June 2007 K. Sundmacher: Electrochemical Energy Conversion using Fuel Cell Systems 1
Research Institutes at Magdeburg/Germany
Otto von Guericke University Fraunhofer Institute for

Magdeburg (11.000 students) Factory Operation and Automation
Experimental
Factory
Max Planck Institute for
Dynamics of Complex
Technical Systems
 1998 started
 4 departments Environmental
 ~ 200 employees Research Center
(UFZ)
World Energy Demand
• Strongly increasing energy

demand, particularly in Asia
• Dependence of many
countries on limited fossile
resources
economic impact:
increasing costs for energy
„harvesting“ and transport
political impact:
fair distribution of resources
• Emissions
local: air polution
global: climate change
Ref.: IEA (International Energy Agency) World Energy Outlook 2002 – Forecast of world energy consumption until 2020.
Solution Strategies
Classical Energy Carriers Renewable Resources

Need for higher efficiencies
Generation
Distribution
Consumption
• Sun
Dispersed power systems: Balancing Availability and • Wind
+ lower losses Demand in Time and Space • Water Flow
+ combined cycles • Geothermal
+ higher net stability Intelligent energy storage • Biomass
- net operation difficult and transport
Solution Strategies

Need for higher efficiencies
Generation
Distribution
Consumption
…how can
Fuel Cells
contribute?
• Sun
+ combined cycles • Earth heat
Solution Strategies: The Role of Fuel Cells

More efficient
production of efficiencies
Need for higher
Generation
electricalDistribution
energy!
Consumption
• Sun

Direct conversion
of Need
Generation
for energy
primary higher efficiencies
at
theDistribution
site of
consumption! Consumption
• Sun

Fuel Cells
Needsuited
ideally for higher
for efficiencies
Generation
combined cycles!
Distribution
Consumption
• Sun

Fuel cells are key
Need for
component inhigher
futureefficiencies
Generation
hydrogen Distribution
economy!
Consumption
• Sun
Working Principle of H2-O2 Fuel Cell (PEMFC)
Hydrogen
Porous
Cathode
Porous Electrolyte
Anode
Polymer Electrolyte Membrane Air
Catalyst Layer
PEM Gas Diffusion Layer
Bipolar Plate
Fuel Cell Stack
Stack UStack = N · Ucell  Stacking N cells in series

-
+ leads to higher voltages.
-
+
-  Larger cross sectional
+
- area A leads to higher
- + currents:
+ IStack = Icell = A · icell,av
100 mm
Single Cell 100 mm

Ucell = 0,5 - 0.9 V
Stack by ZSW, Germany

Electrical Power: 1 kW
Outline
 Introduction
1000 °C  Solid Oxide Fuel Cell: SOFC
600 °C  Molten Carbonate Fuel Cell: MCFC
80 °C  Proton Exchange Membrane Fuel Cell: PEMFC
37 °C  Enzymatic Fuel Cell
 Summary
Working Principle of MCFC
Internal Reforming Anode:

(CH4) Ni-10% Cr
(H2) O2 3 – 6 mm Pores
(CO) N2
CH4 + H2O  CO + 3H2 60 % Porosity
CH4 CO2 (Air)
CO + H2O  CO2 + H2 1 mm Thickness
H2O H2O
H2 + CO32- H2O + CO2 +2e- Cathode:
CO + CO32-  2CO2 +2e- e- NiO
Anode 7 – 15 mm Pores
Catalytic
Electrolyte CO3 2- Electrolyte Matrix:
Ucell Combustion
g-LiAlO2/a-Al2O3
Cathode 0,5 mm Thickness
½O2+CO2+2e-CO32-
Exchaust O2 (N2) Electrolyte:
Air CO2 (H2O) 62% Li2CO3
T = 580 - 650 °C 38% K2CO3
250 kW MCFC Fuel Cell Plant “HotModule”
CO2 / O2
Mixing Fan
Chamber
Catalytic
Fresh Air
Com-
N2 / O2
bustion
Electrical.
Heater FC Stack
HotModule System being installed at
Stainless
Steal Vessel the University Hospital in Magdeburg
Exhaust
Air • Molten Carbonate Fuel Cell: MCFC
Gas
Distributor
• 342 Cells, 250 kW Electrical Power
• ca. 48% Electrical Efficiency
Feed Gas CH 4 / H2O
• Feed Gas: Natural Gas
Developed by: MTU CFC Solutions, Germany
• Size (L x W x H): 7,3 m x 2,5 m x 3,2 m
• Mass  15 t
MCFC Fuel Cell “HotModule”
Fresh Air
Supply
Exhaust Air Cathode Gas Recycle
Anode Effluent
1.2 m
Catalytic
Com-
bustion
System Features:
• 3-dimensional cell stack
• Cross-flow operation
• External recycles
Anode Feed
2D Model of MCFC Fuel Cell “HotModule”
 Enthalpy and Mass Balances of Gas Phases Number

 
 g     , , Convective mass transport,
2x7=14 PDE
  hyperbolic PDE
 
 g     , , Convective energy transport,
2x1=2 PDE
  hyperbolic PDE
g 
0   g  , , Total mass balance,
2x1=2 ODE
 ODE in space
 Enthalpy Balance in Solid Phase

s  2s
  s  ,s ,  
Conductive heat transport,
 1 PDE
  2 parabolic PDE
 Charge Balances at Electrolyte


 i  i a  ,  s ,  
Local charge balance,
2x1= 2 ODE
 ODE in time
 i dA  I
A
cell
Galvanostatic condition,
Integral equation 1 IE
17 PDE, 4 ODE, 1 IE
K. Chudej, P. Heidebrecht, V. Petzet, S. Scherdel, K. Schittkowski, H.J. Pesch, K. Sundmacher, ZAMM 85 (2005) 132-140.
Steady State MCFC Simulation Results
Average Current Density: 125 mA/cm²; S/C = 2.5; Fuel Utilization: 70%
P. Heidebrecht, K. Sundmacher, Hydrogen at Anode

Journal of the Electrochemical Society 152, 2005, A2217-2228.
Anode Cathode
Feed Feed
CH4 / H2O O2 / CO2
Current Density Temperature at Cathode
Dynamic Response to Load Change
Icell
0.85
0.7

step=0.1 =500
Heat
Transport
Cell Voltage, Ucell
in Solid
Parts
Double Mass
Layer Transfer to
Charging Electrodes
P. Heidebrecht, K. Sundmacher,
Journal of the Electrochemical Society 152, 2005, A2217-2228.
Time,  - step
Model-based Observer
 Measurable: cell voltage,

gas exit temperatures,
gas exit compositions
?
 Desirable for process control
and monitoring: Information
on internal temperatures
and gas compositions
 very difficult to measure!
 Solution:
Observer / State Estimator
MCFC
Sensoren
? y
Inputs u
Real States x Outputs y

Process
Observer Correction
x̂(  )  x̂(  ) +
 k  y  ŷ 
-
tmess
ŷ
x̂t 
f  x̂ , x̂ z ,
ŷ  h( x̂ )
!
Observer x̂  x
MCFC Model Sensor Models
• Experimental results: Estimation Experimental Data
Experimental Information for

Filter Validation
 Good Precision of
State Estimation
Experimental Information for

Filter Correction
 Good Filter Convergence
Outline
 Introduction
 Summary
SOFC: Candidate for Steady State Power Plants
DC/AC Converter
SOFC: Solid Oxide Fuel Cell
USV
Electrolyte: Solid Oxide Ceramics (YSZ) Gas Feed
Effectiveness: 55 – 65 %
Temperature: 800 - 1000 °C
Future Use: Power plants for kW - GW range
Electrical Switches
Anode
Solid Oxide Cathode
Cathode Contactors
Electrolyte
Cathode
Source: Siemens-Westinghouse,
www.powergeneration.siemens.com/en/fuelcells Air Anode
Temperature Effects in Electrical Conductors
- +
current current
density density
+ -
Metallic Conductor Oxygen Ion Conductor (Fuel Cell)

• Charge transport by electrons • Charge transport by ions
• Electrical conductivity decreases at • Electrical conductivity increases at
increasing temperature increasing temperature
• If local temperature increases: • If local temperature increases:
 local current density decreases  local current density increases
 local heat production decreases  local heat production increases
(Ohmic losses) (Ohmic losses + reaction heat)
 self-stabilizing effect  de-stabilizing effect
Mangold, M., Krasnyk, K., Sundmacher, K., Chemical Engineering Science 59 (2004) 4869 - 4877
Simple 1D Model for SOFC
Model asumptions:
 1D approach (gradients only in y-direction)
 Heat transport via heat conduction (Fourier’s law)
 Concentration polarization neglected
 Infinitely high electrical conductivity of electrodes
 Arrhenius-type temperature dependence of electrical conductivity
SOFC: Dimensionsless Model Equations
  2
• Energy balance:  2  B i  Ucell  i  Bi1  
 
 
• Boundary conditions:  Bi 2 ( 0, )  Bi 2 ( 1, )
 0,  1,
• Electrochemical kinetics at anode and cathode:

 A / C    eq    A / C eq  A / C 
A/C
i  A/C
exp  g exp   (1   )g
A/C
  K eq exp   g
A/C

 1     1    1   
• Ohm’s law for ion transport in 

i   E exp  g E
  A
 1 
   
C

tot

electrolyte:
1
• Overall charge balance for electrodes: I tot  i d
0
Arrhenius term
SOFC: Phase Portrait at Ucell = const.
Solutions for a fuel cell of infinite length:
 Periodic solutions
along space
coordinate possible!
SOFC: Phase Portrait at Ucell = const.
Solutions for a fuel cell of finite length:

left boundary:

 Bi2(0, )
 0
right boundary:

  Bi2(0, )
 0
SOFC: Current Instabilities at Icell = const.
g E1 gE2> gE1
gE3> gE2
Outline
 Introduction
 Summary
PEMFC: Use in Mobile Applications
PEMFC: Polymer Electrolyte Membrane Fuel Cell

Electrolyte: Polymeric Membrane as Ion Conductor
Efficiency: 30 - 50%
Temperature: 20 - 100 °C (Goal: 180 °C)
Use: Cars, portable devices, battery substitute
H2
Anode
PEM H+
Cathode e-
O2 H2O
Problem: Membrane Water Management
Source: Adam Opel AG Opel HydroGen 3 (2001) H2-operation, 150 km/h, 400 km distance
PEMFC: Multiple Steady Operating States
PEM Fuel Cell: H2 + ½ O2  H2O

Map of Operating Modi
Gas Humidity
Water production curve:

 ( a H 2O )
 PROD (a H 2O ) 
rL   (a H 2O )  c

Water removal line:

 REM (aH O )   pHsatO aH O  pH O,in 
2 2 2 2
Hydrogen Feed Flow
Water activity in membrane, aH2O Hanke, Mangold, KS, Fuel Cells 5 (2005) 133
Hanke-Rauschenbach, Mangold, KS, JPS (2006) in prep.
PEMFC: Nonlinear Operating Dynamics
Current Voltage Curve
Humidity
reduction
Response behaviour at load variations
R. Hanke-Rauschenbach, M. Mangold,
K. Sundmacher, JPS (2006) in prep.
R. Hanke-Rauschenbach, M. Mangold,
K. Sundmacher, AIChE Meeting,
San Francisco, 12-17 Nov. 2006.
Outline
 Introduction
 Summary
Enzymatic Fuel Cells:
Possible Biomedical Applications
Hearing Devices
Pacemakers
Neuro-Stimulators
ICD/CHF Devices LVAD Artificial

Hearts
Insulin Pumps Drug Pumps
Incontinence Devices
Bone Growth Stimulators

 Goal:
Implantable fuel cell in
the mW to W range
Redox Processes in Biology
Oxidation
-D-glucose -gluconolactone gluconic acid
CH2OH CH2OH CH2OH
FAD
O OH O OH
H2O
OH OH O OH
OH OH OH COOH
-
OH +2e OH OH
+2H+
FAD FADH2 FAD =

Flavin Adenin Dinucleotid
-2e-
-2H+ is a redox cofactor
H2O2 O2
of the enzyme
Reduction
Glucose Oxidase
Glucose Oxidase, GOX
Enzymatic Fuel Cell: Working Principle
Anode: C6H12O6
C6H10O6 + 2e- + 2H+ Oxidation E = - 0.5 V
Cathode: ½ O2 + 2e- + 2H+ H 2O Reduction E = 0.7 V
Overall: C6H12O6 + ½ O2 C6H10O6 + H2O ΔE = 1.2 V
ANODE e- Voltage
Cathode
Anode
H2O
gluconic acid
Immobilisation
H+
enzymes e-
e-
redox center O2
Electron transfer glucose Current ~ Enzymes per Area
Enzyme
Fuel Oxidant
+
H
e- e-
Membrane
H 2O
Oxidized Product
Enzyme
Anode Cathode
K. Sundmacher: Electrochemical Energy Conversion using Fuel Cell Systems

EFC
Cell design
and Hybrid EFC
optimization
Optimization Combined
Optimum cell
of membrane with MFC
configurations
and electrodes and/or battery
K. Sundmacher: Electrochemical Energy Conversion using Fuel Cell Systems

Immobilisation of Glucose Oxidase
at Gold Electrode
COOH
HOOC HN
PQQ = Mediator: redox-active component
for electron transfer between enzyme and
electrode
HOOC N O
NH2
S
NH2 H2N FAD
S PQQ
S NH2 S NH PQQ
EDC, NHS EDC, NHS
Au glucose
apo-GOX e-
S NH PQQ NH
FAD S NH PQQ NH
FAD
e- gluconic
acid
Enzyme Electrode: Proof of Principle with Glucose
apo-GOX e- glucose
S NH PQQ NH
FAD S NH PQQ NH
FAD
gluconic
e- acid
Onset potential
Thermodynamic
potential
Overpotentia
l
Summary: Important Trends in Fuel Cell Engineering
High temperature fuel cells:

 Molten Carbonate fuel cells (HotModule) are very close to the market
 Efficient co-production of electricity and heat
 Internal direct reforming (DIR) is most attractive process variant
Low temperature fuel cells:

 PEMFC: Problem of water management in membranes
 Development of water-free membranes for mobile applications
Enzymatic fuel cells:

 Biomedical applications: interdisciplinary collaboration between
chemical engineering, electrochemistry and organic chemistry
necessary

Sundmacher NTNU 2007

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Electrochemical Energy Conversion

using Fuel Cell Systems

Otto von Guericke University Fraunhofer Institute for

• Strongly increasing energy

Classical Energy Carriers Renewable Resources

Classical Energy Carriers Renewable Resources

Classical Energy Carriers Renewable Resources

Classical Energy Carriers Renewable Resources

Classical Energy Carriers Renewable Resources

Classical Energy Carriers Renewable Resources

Stack UStack = N · Ucell  Stacking N cells in series

Single Cell 100 mm

Stack by ZSW, Germany

1000 °C  Solid Oxide Fuel Cell: SOFC

600 °C  Molten Carbonate Fuel Cell: MCFC

80 °C  Proton Exchange Membrane Fuel Cell: PEMFC

37 °C  Enzymatic Fuel Cell

Internal Reforming Anode:

 Enthalpy and Mass Balances of Gas Phases Number

 Enthalpy Balance in Solid Phase

 Charge Balances at Electrolyte

P. Heidebrecht, K. Sundmacher, Hydrogen at Anode

Current Density Temperature at Cathode

 Measurable: cell voltage,

Real States x Outputs y

• Experimental results: Estimation Experimental Data

Experimental Information for

Experimental Information for

1000 °C  Solid Oxide Fuel Cell: SOFC

600 °C  Molten Carbonate Fuel Cell: MCFC

80 °C  Proton Exchange Membrane Fuel Cell: PEMFC

37 °C  Enzymatic Fuel Cell

Metallic Conductor Oxygen Ion Conductor (Fuel Cell)

• Electrochemical kinetics at anode and cathode:

• Ohm’s law for ion transport in 

Solutions for a fuel cell of infinite length:

Solutions for a fuel cell of finite length:

1000 °C  Solid Oxide Fuel Cell: SOFC

600 °C  Molten Carbonate Fuel Cell: MCFC

80 °C  Proton Exchange Membrane Fuel Cell: PEMFC

37 °C  Enzymatic Fuel Cell

PEMFC: Polymer Electrolyte Membrane Fuel Cell

Problem: Membrane Water Management

PEM Fuel Cell: H2 + ½ O2  H2O

Water production curve:

Water removal line:

Current Voltage Curve

Response behaviour at load variations

1000 °C  Solid Oxide Fuel Cell: SOFC

600 °C  Molten Carbonate Fuel Cell: MCFC

80 °C  Proton Exchange Membrane Fuel Cell: PEMFC

37 °C  Enzymatic Fuel Cell

ICD/CHF Devices LVAD Artificial

Insulin Pumps Drug Pumps

Bone Growth Stimulators

FAD FADH2 FAD =

Glucose Oxidase, GOX

Overall: C6H12O6 + ½ O2 C6H10O6 + H2O ΔE = 1.2 V

K. Sundmacher: Electrochemical Energy Conversion using Fuel Cell Systems

K. Sundmacher: Electrochemical Energy Conversion using Fuel Cell Systems

High temperature fuel cells:

Low temperature fuel cells:

Enzymatic fuel cells: